US20240209166A1 - Resin composition for non-conductive film with excellent high temperature properties for 3d tsv packages - Google Patents

Resin composition for non-conductive film with excellent high temperature properties for 3d tsv packages Download PDF

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US20240209166A1
US20240209166A1 US18/416,190 US202418416190A US2024209166A1 US 20240209166 A1 US20240209166 A1 US 20240209166A1 US 202418416190 A US202418416190 A US 202418416190A US 2024209166 A1 US2024209166 A1 US 2024209166A1
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film
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composition
group
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Jie Bai
Qizhuo Zhuo
James Sungwook Jang
Kyu Chang Shim
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • H01L23/295—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
    • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • compositions for forming films and the use of said films in three-dimension through-silicon-via (3D TSV) packages relate to compositions comprising one or more resins, one or more imidazoles with latent thermal activity, one or more inorganic fillers, and one or more additives, to B-stage films prepared from the disclosed compositions, and to cured films obtained after cure of the disclosed compositions.
  • cured films obtained after cure of the disclosed compositions have particular physical properties and/or combinations of physical properties.
  • the disclosure relates to underfill films prepared from disclosed compositions, such as wafer-level underfill films (WAUFs).
  • WAUFs wafer-level underfill films
  • Embodiments of the disclosed films are suitable for, for example, use in thermal compression bonding processes.
  • the materials industry faces the need to improve the high temperature properties of film materials (e.g., underfill film materials).
  • film materials e.g., underfill film materials.
  • the realization of this goal may bring such benefits as higher thermal stability and, consequently, higher reliability in applications across the automotive, computing, networking, and telecommunication industries.
  • Features that may be associated with improved high temperature properties of film materials include a comparatively high Tg (glass transition temperature), a comparatively low CTE (coefficient of thermal expansion), and a comparatively high modulus at, e.g., 250° C.
  • B-stage films prepared from certain conventional resin compositions comprising maleimide-containing resins may have a DSC onset temperature that is less than 100° C. to 150° C.
  • the bondhead contact temperature becomes from 100° C. to 150° C. (e.g., as occurs in a process where a bondhead contact temperature is from 130° C. to 210° C.)
  • material entrapment issues can arise at solder joints.
  • B-stage films prepared from conventional resin compositions comprising maleimide-containing resins may have a DSC onset temperature that is greater than the melting temperature of solder (e.g., lead-free solder), such as a DSC onset temperature that is greater than, for example, 217° C.
  • solder e.g., lead-free solder
  • solder extrusion issues may arise.
  • solder extrusion issues may also arise where a B-stage film prepared from a conventional resin composition comprising one or more maleimide-containing resins has a ⁇ T from the DSC onset temperature to the DSC peak temperature that is, for example, greater than 20° C., such as about 40° C.
  • compositions comprising one or more resins, one or more inorganic fillers, and one or more additives, to B-stage films prepared from said compositions, and to cured films obtained after cure of said compositions, wherein said compositions comprise one or more imidazoles with latent thermal activity.
  • an imidazole with latent thermal activity refers to an imidazole that, when combined in the amount of 0.20 g with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), yields a composition that, when measured on a TA Instruments Thermal Analyzer DSC Q20 in N 2 , from room temperature to 300° C.
  • an imidazole with latent thermal activity when analyzed as just described, exhibits a DSC onset temperature of at least 145° C., at least 150° C., at least 155° C., at least 160° C., at least 165° C., at least 170° C., at least 175° C., or at least 180° C.
  • an imidazole with latent thermal activity when analyzed as just described, exhibits a DSC onset temperature of from 145° C.
  • to 180° C. such as from 145° C. to 175° C., 145° C. to 170° C., 145° C. to 160° C., 150° C. to 180° C., 150° C. to 175° C., 150° C. to 170° C., 150° C. to 160° C., 155° C. to 175° C., 155° C. to 170° C., or from 155° C. to 165° C.
  • an imidazole with latent thermal activity when analyzed as just described, exhibits a DSC peak temperature of at least 150° C., at least 155° C., at least 160° C., at least 165° C., at least 170° C., at least 175° C., or at least 185° C.
  • an imidazole with latent thermal activity when analyzed as just described, exhibits a DSC peak temperature of from 150° C. to 185° C., such as from 150° C. to 180° C., 150° C. to 175° C., 150° C. to 170° C., 150° C. to 165° C., 150° C. to 160° C., 160° C. to 180° C., 165° C. to 175° C., or 160° C. to 170° C.
  • the DSC onset temperature and/or DSC peak temperature exhibited by a composition prepared and measured as just described may be the same as or different from the DSC onset temperature and/or DSC peak temperature exhibited by a composition comprising the same imidazole with latent thermal activity but with other components, such as one or more resins, or more inorganic fillers, and/or one or more additives.
  • an imidazole with latent thermal activity comprises at least two electron-withdrawing groups.
  • imidazoles that do not constitute imidazoles with latent thermal activity include those that, when combined in the amount of 0.20 g with 1.0 g of NC-3000-L epoxy resin (Nippon Kayaku), yield a composition that, when measured on a TA Instruments Thermal Analyzer DSC Q20 in N 2 , from room temperature to 300° C. and at a 10° C./min ramping rate, exhibits a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C.
  • Imidazole A is 4-methyl-2-phenyl-1H-imidazole-5-methanol.
  • Imidazole B is 2-phenyl-4,5-dihydroxymethylimidazole.
  • Imidazole C is 2-phenylimidazole.
  • Imidazole D is 2-ethyl-4-methyl-1H-imidazole-1-propanenitrile.
  • Imidazole A and Imidazole B are exemplary imidazoles with latent thermal activity, whereas Imidazole C and Imidazole D are not considered imidazoles with latent thermal activity within the context of this disclosure.
  • the compositions comprising Imidazole A or Imidazole B each exhibited a DSC onset temperature at least 145° C. and a DSC peak temperature of at least 150° C.
  • the compositions comprising Imidazole C or Imidazole D each exhibited a DSC onset temperature of less than 145° C. and a DSC peak temperature of less than 150° C.
  • Embodiments of the disclosed compositions address issues discussed above.
  • embodiments of underfill films prepared from disclosed compositions are suitable for thermal compression bonding processes, such as thermal compression bonding processes for 3D TSV stacking applications.
  • embodiments of underfill films prepared from disclosed compositions exhibit one or more of good die corner coverage, gap filling, and electrical interconnect joint formation.
  • aspects of the present disclosure are directed to:
  • FIG. 1 presents DSC (differential scanning calorimetry) data for an exemplary composition of the disclosure (Inventive Example 3).
  • FIG. 2 presents melt viscosity data for an exemplary composition of the disclosure (Inventive Example 3).
  • FIG. 3 presents DMA (dynamic mechanical analysis) data for an exemplary composition of the disclosure (Inventive Example 3).
  • FIG. 4 presents TMA (thermomechanical analysis) data for an exemplary composition of the disclosure (Inventive Example 3).
  • FIG. 5 presents DSC (differential scanning calorimetry) data for an exemplary composition of the disclosure (Inventive Example 8).
  • FIG. 6 presents melt viscosity data for an exemplary composition of the disclosure (Inventive Example 8).
  • FIG. 7 presents DMA (dynamic mechanical analysis) data for an exemplary composition of the disclosure (Inventive Example 8).
  • FIG. 8 presents TMA (thermomechanical analysis) data for an exemplary composition of the disclosure (Inventive Example 8).
  • compositions and processes may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures, which form a part of this disclosure.
  • compositions comprising one or more resins, one or more imidazoles with latent thermal activity, one or more inorganic fillers, and one or more additives.
  • the one or more resins are selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins.
  • the one or more additives selected from the group consisting of adhesion promoters and film formers.
  • the one or more imidazoles with latent thermal activity are one or more imidazoles comprising at least two electron withdrawing groups.
  • the film after the composition forms a film, the film has certain features and/or properties that make the film suitable for use in thermal compression bonding processes.
  • the film after the composition forms a film, the film has a Tg of >100° C. as measured by dynamic mechanical analysis (DMA), a storage modulus at 25° C. of ⁇ 4 GPa, a storage modulus at 250° C.>0.1 GPa, and a coefficient of thermal expansion (CTE) ⁇ 250 ppm/° C.
  • DMA dynamic mechanical analysis
  • CTE coefficient of thermal expansion
  • the B-stage film after the composition forms a B-stage film, the B-stage film has a differential scanning calorimetry (DSC) onset temperature from 130° C. to 250° C.
  • DSC differential scanning calorimetry
  • the cured film has a Tg of >100° C., >125° C., >150° C., >160° C., >165° C., >170° C.>175° C., >180° C., >185° C., >190° C., >200° C., >210° C., >220° C., >230° C., >240° C., >250° C., >260° C., >270° C., >280° C., >290° C., or >300° C., each as measured by dynamic mechanical analysis (DMA).
  • DMA dynamic mechanical analysis
  • the cured film has a Tg of from 100° C. to 110° C., from 110° C. to 120° C., from 120° C. to 130° C., from 130° C. to 140° C., from 140° C. to 150° C., from 150° C. to 160° C., from 160° C. to 170° C., from 170° C. to 180° C., from 180° C. to 190° C., from 190° C. to 200° C., from 200° C. to 210° C., from 210° C. to 220° C., from 220° C. to 230° C., from 230° C.
  • the cured film has a Tg of >100° C., >125° C., >150° C., >160° C., >165° C., >170° C., >175° C., >180° C., >185° C., >190° C., >200° C., >210° C., >220° C., >230° C., >240° C., or >250° C., each as measured by thermomechanical analysis (TMA).
  • TMA thermomechanical analysis
  • the cured film has a Tg of from 100° C. to 110° C., from 110° C. to 120° C., from 120° C.
  • the cured film has a Tg of from 140° C. to 200° C., such as from 150° C. to 190° C., from 160° C. to 190° C., or from 160° C. to 180° C.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 25° C. of ⁇ 3 GPa, ⁇ 3.5 GPa, ⁇ 4 GPa, ⁇ 4.5 GPa, ⁇ 5 GPa, ⁇ 5.5 GPa, ⁇ 6 GPa, or ⁇ 6.5 GPa.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 25° C. of from 2.0 GPa to 3.0 GPa, from 3.0 GPa to 3.5 GPa, from 3.5 GPa to 4.0 GPa, from 4.0 GPa to 4.5 GPa, from 4.5 GPa to 5.0 GPa, from 5.0 GPa to 5.5 GPa, from 5.5 GPa to 6.0 GPa, or from 6.0 GPa to 6.5 GPa.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 25° C. of from 3.0 GPa to 6.5 GPa.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 25° C. of from 3.5 GPa to 6.0 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 25° C. of from 4.0 GPa to 5.5 GPa.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 250° C. of >0.1 GPa, >0.2 GPa, >0.3 GPa, >0.4 GPa, >0.5 GPa, >0.6 GPa, >0.7 GPa, >0.8 GPa, >0.9 GPa, >1.0 GPa, or >1.1 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C.
  • the B-stage film has a storage modulus at 250° C. of from 0.4 GPa to 1.2 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C. of from 0.4 GPa to 1.2 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 250° C. of from 0.5 GPa to 1.2 GPa.
  • the B-stage film after the composition forms a B-stage film, has a storage modulus at 230° C. of >0.1 GPa, >0.2 GPa, >0.3 GPa, or >0.4 GPa, >0.5 GPa, >0.6 GPa, >0.7 GPa, >0.8 GPa, >0.9 GPa, >1.0 GPa, >1.1 GPa, or >1.2 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 230° C.
  • the B-stage film has a storage modulus at 230° C. of from 0.5 GPa to 1.2 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 230° C. of from 0.5 GPa to 1.2 GPa. In some embodiments, after the composition forms a B-stage film, the B-stage film has a storage modulus at 230° C. of from 0.6 GPa to 1.2 GPa.
  • the cured film has a coefficient of thermal expansion (CTE) ⁇ 60 ppm/oC, ⁇ 70 ppm/oC, ⁇ 80 ppm/° C., ⁇ 90 ppm/oC, ⁇ 100 ppm/oC, ⁇ 110 ppm/oC, ⁇ 120 ppm/oC, ⁇ 130 ppm/oC, ⁇ 140 ppm/° C., ⁇ 150 ppm/oC, ⁇ 160 ppm/oC, ⁇ 170 ppm/oC, ⁇ 180 ppm/° C., ⁇ 190 ppm/° C., ⁇ 200 ppm/° C., ⁇ 210 ppm/oC, ⁇ 220 ppm/oC, ⁇ 230 ppm/° C., ⁇ 240 ppm/oC, or ⁇ 250 ppm/oC.
  • CTE coefficient of thermal expansion
  • the cured film has a coefficient of thermal expansion (CTE) above Tg ⁇ 100 ppm/° C., ⁇ 110 ppm/oC, ⁇ 120 ppm/° C., ⁇ 130 ppm/° C., ⁇ 140 ppm/oC, ⁇ 150 ppm/° C., ⁇ 160 ppm/° C., ⁇ 170 ppm/oC, ⁇ 180 ppm/oC, ⁇ 190 ppm/oC, ⁇ 200 ppm/oC, ⁇ 210 ppm/oC, ⁇ 220 ppm/oC, ⁇ 230 ppm/oC, ⁇ 240 ppm/° C., or ⁇ 250 ppm/° C.
  • CTE coefficient of thermal expansion
  • the cured film has a coefficient of thermal expansion (CTE) above Tg from 50 ppm/° C. to 80 ppm/° C. In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg from 60 ppm/° C. to 80 ppm/° C. In some embodiments, after the composition forms a cured film, the cured film has a coefficient of thermal expansion (CTE) above Tg from 60 ppm/° C. to 70 ppm/° C.
  • CTE coefficient of thermal expansion
  • the B-stage film after the composition forms a B-stage film, has a minimum film melt viscosity from 500 Pa ⁇ s to 8,000 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity from 900 Pa ⁇ s to 6,500 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 .
  • the B-stage film after the composition forms a B-stage film, has a minimum film melt viscosity from 2,000 Pa ⁇ s to 6,000 Pa's as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity from 2,000 Pa ⁇ s to 4,000 Pa's as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 .
  • the B-stage film has a minimum film melt viscosity from 4,000 Pa ⁇ s to 6,000 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 .
  • the B-stage film has a minimum film melt viscosity from 500 Pa ⁇ s to 600 Pa ⁇ s, from 600 Pa ⁇ s to 700 Pa ⁇ s, from 700 Pa ⁇ s to 800 Pa ⁇ s, from 800 Pa ⁇ s to 900 Pa ⁇ s, from 900 Pa ⁇ s to 1,000 Pa ⁇ s, from 1,000 Pa ⁇ s to 1,100 Pa ⁇ s, from 1,100 Pa ⁇ s to 1,200 Pa ⁇ s, from 1,200 Pas to 1,300 Pa ⁇ s, from 1,300 Pa ⁇ s to 1,400 Pa ⁇ s, from 1,400 Pa ⁇ s to 1,500 Pa ⁇ s, from 1,500 Pa ⁇ s to 1,600 Pa ⁇ s, from 1,600 Pa ⁇ s to 1,700 Pa ⁇ s, from 1,700 Pa ⁇ s to 1,800 Pa ⁇ s, from 1,800 Pa ⁇ s to 1,900 Pa ⁇ s, from 1,900 Pa ⁇ s to 2,000 Pa ⁇ s, from 2,000 Pa ⁇ s to 2,100 Pas, from 2,100 Pa ⁇ s to 2,200 Pa ⁇ s, from 2,200 Pa ⁇ s to 2,300 Pa ⁇ s, from 2,300
  • the B-stage film after the composition forms a B-stage film, has a minimum film melt viscosity from 400 Pa ⁇ s to 7,000 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a minimum film melt viscosity from 500 Pa ⁇ s to 8,000 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 .
  • the B-stage film has a differential scanning calorimetry (DSC) onset temperature of from 130° C. to 140° C., from 140° C. to 150° C., from 150° C. to 160° C., from 160° C. to 170° C., from 170° C. to 180° C., from 180° C. to 190° C., from 190° C. to 200° C., from 200° C. to 210° C., from 210° C. to 220° C., from 220° C. to 230° C., from 230° C. to 240° C., or from 240° C. to 250° C., as measured by DSC with a 10° C./min ramping rate in N 2 .
  • DSC differential scanning calorimetry
  • the B-stage film has a differential scanning calorimetry (DSC) onset temperature of from about 130° C. to about 140° C., from about 140° C. to about 150° C., from about 150° C. to about 160° C., from about 160° C. to about 170° C., from about 170° C. to about 180° C., from about 180° C. to about 190° C., from about 190° C. to about 200° C., from about 200° C. to about 210° C., from about 210° C. to about 220° C., from about 220° C. to about 230° C., from about 230° C. to about 240° C., or from about 240° C. to about 250° C., as measured by DSC with a 10° C./min ramping rate in N 2 .
  • DSC differential scanning calorimetry
  • the B-stage film has a DSC onset temperature from 150° C. to 190° C. as measured by DSC with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a DSC onset temperature from 140° C. to 180° C. as measured by DSC with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a DSC onset temperature from 150° C. to 180° C. as measured by DSC with a 10° C./min ramping rate in N 2 .
  • the B-stage film has a DSC onset temperature from 140 to 160° C. as measured by DSC with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a DSC onset temperature from 140 to 150° C. as measured by DSC with a 10° C./min ramping rate in N 2 . In some embodiments, after the composition forms a B-stage film, the B-stage film has a DSC onset temperature from 170 to 180° C. as measured by DSC with a 10° C./min ramping rate in N 2 .
  • the B-stage film has a ⁇ T from the DSC onset temperature to the DSC peak temperature that is less than 20° C., less than 15° C., less than 10° C., or less than 5° C. In some embodiments, after the composition forms a B-stage film, the B-stage film has a ⁇ T from the DSC onset temperature to the DSC peak temperature that is from 0° C. to 5° C., from 5° C. to 10° C., from 10° C. to 15° C., or from 15° C. to 20° C.
  • the B-stage film has a ⁇ T from the DSC onset temperature to the DSC peak temperature that is 0° C., 1° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., or 20° C.
  • a ⁇ T from the DSC onset temperature to the DSC peak temperature that is less than 20° C., less than 15° C., less than 10° C., or less than 5° C., or that is from 0° C. to 5° C., from 5° C. to 10° C., from 10° C. to 15° C., or from 15° C. to 20° C. represents fast curing kinetics that, for example, prevent solder extrusion (a phenomenon that, in at least some embodiments, makes a composition less suitable or unsuitable for thermal compression bonding) from occurring.
  • a B-stage film having a ⁇ T from the DSC onset temperature to the DSC peak temperature that is greater than or equal to 20° C. is not suitable for thermal compression bonding processes.
  • certain B-stage films prepared from compositions that comprise a bis-maleimide resin, an epoxy resin, and 4,4-diaminodiphenyl sulfone but that do not comprise one or more imidazoles with latent thermal activity e.g., one or more imidazoles comprising at least two electron withdrawing groups, such as imidazoles comprising at least two electron withdrawing groups as disclosed herein
  • the present disclosure refers to certain organic groups as being, in some embodiments, “substituted.”
  • substituted means that the subject organic group bears one or more substituents, where a substituent is an atom or a group of atoms that replaces a hydrogen atom on the subject organic group.
  • a substituent may replace one or more hydrogen atoms, ranging from replacement of exactly one hydrogen atom to the replacement of all hydrogen atoms on the subject organic group.
  • an organic group may bear multiple substituents, the substituents are selected independently and can be, but need not be, identical.
  • the present disclosure refers to certain organic groups as being, in some embodiments, “unsubstituted.”
  • the term “unsubstituted” means that the subject organic group bears no substituents (as that term is described above).
  • compositions of the disclosure include, among other constituents, one or more imidazoles comprising at least two electron withdrawing groups.
  • the imidazole comprising at least two electron withdrawing groups is a substituted imidazole comprising a substituent on the 2-position and optionally a substituent on the 4-position, a substituent on the 5-position, and/or a substituent on the nitrogen at the 1-position.
  • the imidazole comprising at least two electron withdrawing groups is a substituted imidazole comprising an electron-withdrawing substituent (alternatively referred to herein as an electron-withdrawing group) on the 2-position and optionally a substituent on the 4-position, a substituent on the 5-position, and/or a substituent on the nitrogen at the 1-position.
  • an electron-withdrawing substituent alternatively referred to herein as an electron-withdrawing group
  • Exemplary electron withdrawing groups include, but are not limited to, substituted or unsubstituted aryl groups (e.g., phenyl), cyano (—CN), halide (—X) (e.g., fluoro (—F), bromo (—Br), and iodo (—I)), —CHO, —COOH, and amino (—NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from a hydrogen atom or a substituted or unsubstituted alkyl group), alkyl groups substituted with one or more groups independently selected from cyano (—CN), halide (—X) (e.g., fluoro (—F), bromo (—Br), and iodo (—I)), —CHO, —COOH, and amino (—NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from a hydrogen atom or a substituted or unsubstituted alkyl group), and oxygen
  • electron withdrawing groups reduce electron density on the imidazole ring (e.g., at the tertiary nitrogen of the imidazole) and/or attenuate the reactivity of the imidazole (e.g., attenuate the reactivity of the tertiary nitrogen of the imidazole).
  • the imidazole is represented by Formula (I)
  • the imidazole comprises at least two electron-withdrawing groups independently selected from the group consisting of substituted or unsubstituted aryl groups (e.g., phenyl), cyano (—CN), halide (—X) (e.g., fluoro (—F), bromo (—Br), and iodo (—I)), —CHO, —COOH, amino (—NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from a hydrogen atom or a substituted or unsubstituted alkyl group), alkyl groups substituted with one or more groups independently selected from cyano (—CN), halide (—X) (e.g., fluoro (—F), bromo (—Br), and iodo (—I)), —CHO, —COOH, and amino (—NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from a hydrogen atom or a substituted or un
  • the imidazole comprises at least two electron-withdrawing groups independently selected from the group consisting of hydroxymethyl and phenyl.
  • the imidazole comprises at least two electron-withdrawing groups independently selected from organic groups that reduce electron density on the imidazole ring and/or attenuate the reactivity of the imidazole.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 1 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, and substituted or unsubstituted C 6 -C 10 aryl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 1 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, substituted C 6 aryl, and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 1 is selected from the group consisting of H and substituted or unsubstituted C 1 -C 6 alkyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 1 is selected from the group consisting of H and unsubstituted C 1 -C 6 alkyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 1 is H.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 2 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, and substituted or unsubstituted C 6 -C 10 aryl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 2 is selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, substituted C 6 aryl, and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 2 is selected from the group consisting of substituted or unsubstituted C 1 -C 6 alkyl, substituted C 6 aryl, and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 2 is selected from the group consisting of unsubstituted C 1 -C 6 alkyl and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 2 is phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, and substituted or unsubstituted C 6 -C 10 aryl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of H, substituted or unsubstituted C 1 -C 6 alkyl, substituted C 6 aryl, and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted or unsubstituted C 1 -C 6 alkyl, substituted C 6 aryl, and phenyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted or unsubstituted C 1 -C 6 alkyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl, wherein each independently selected substituted C 1 -C 6 alkyl is substituted with one or more substituents selected from the group consisting of halogen, hydroxy, cyano, C 1 -C 6 alkoxy, carboxylic acid, ester (e.g., —C(O)OR 5 , wherein R 5 is a substituted or unsubstituted alkyl group), ketone (e.g., —C(O)R 6 , wherein R 6 is a substituted or unsubstituted alkyl group), amido (e.g., —C(O)N(R 7 )(R 8 ), wherein each of R 7 and R 8 is independently selected from the group consisting of H, substituted alkyl, and unsubstituted alkyl),
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl, wherein each independently selected substituted C 1 -C 6 alkyl is substituted with one or more substituents selected from the group consisting of halogen, hydroxy, cyano, C 1 -C 6 alkoxy, and carboxylic acid.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl, wherein each independently selected substituted C 1 -C 6 alkyl is substituted with one or more substituents selected from the group consisting of halogen, hydroxy, and C 1 -C 6 alkoxy.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl, wherein each independently selected substituted C 1 -C 6 alkyl is substituted with one or more hydroxy groups.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein R 3 and R 4 are each independently selected from the group consisting of substituted C 1 -C 6 alkyl, wherein each independently selected substituted C 1 -C 6 alkyl is substituted with exactly one hydroxy group.
  • the imidazole comprising at least two electron withdrawing groups is represented by Formula (I) wherein:
  • the imidazole comprising at least two electron withdrawing groups is represented by:
  • the imidazole comprising at least two electron withdrawing groups is represented by:
  • compositions according to the disclosure comprise adducts of one or more imidazoles as described herein with one or more agents. In some embodiments, these imidazole adducts dissociate thermally to release one or more imidazoles.
  • the one or more imidazoles with latent thermal activity are included in amounts ranging from about 0.5 wt. % to about 10 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 1 wt. % to about 8 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2 wt. % to about 7 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2.5 wt. % to about 6.5 wt. %.
  • the one or more imidazoles with latent thermal activity are included in amounts ranging from about 3 wt. % to about 6 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2.5 wt. % to about 4.5 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 1 wt. % to about 4 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2 wt. % to about 4 wt. %.
  • the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2 wt. % to about 3.5 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2 wt. % to about 3 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity are included in amounts ranging from about 2.5 wt. % to about 3.5 wt. %. In some embodiments, the one or more imidazoles with latent thermal activity referred to in this paragraph are one or more imidazoles comprising at least two electron withdrawing groups.
  • the maleimide-containing resin, nadimide-containing resin, or itaconimide-containing resin is represented by, respectively:
  • J is a monovalent or polyvalent radical selected from:
  • J is substituted or unsubstituted C 6 aryl, oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheterocyclic, carb
  • the maleimide-containing resin is represented by
  • the composition comprises a compound represented by
  • This compound is BMI-5100 (chemical name: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide; Daiwa Kasei, Japan), which is a compound that has an average number molecular weight of around 300 tested by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the maleimide-containing resin is represented by
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight from 180 to 400.
  • a maleimide equivalent weight is the weight of resin in grams which contains one equivalent of maleimide functional group.
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight of 220.
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight of 300.
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight of about 400.
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight from about 390 to about 400.
  • the maleimide-containing resin is a BMI resin with a maleimide equivalent weight from 390 to 400.
  • maleimide-containing resins are included in amounts ranging from about 1 wt. % to about 20 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 1 wt. % to about 15 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 3 wt. % to about 15 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 1 wt. % to about 5 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 5 wt. % to about 20 wt. %.
  • maleimide-containing resins are included in amounts ranging from about 5 wt. % to about 15 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 10 wt. % to about 20 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 10 wt. % to about 15 wt. %. In some embodiments, maleimide-containing resins are included in amounts ranging from about 12 wt. % to about 17 wt. %. In some embodiments, maleimide-containing resins are included in about 10 wt. %, about 11 wt. %, about 12 wt.
  • the itaconimide-containing resin is represented by:
  • Ar is a substituted or substituted aryl group.
  • the itaconimide-containing resin is:
  • the nadimide is represented by:
  • compositions of the disclosure include, among other constituents, one or more epoxy resins.
  • epoxy-functionalized resins are contemplated for use herein, e.g., liquid-type epoxy resins based on bisphenol A, solid-type epoxy resins based on bisphenol A, liquid-type epoxy resins based on bisphenol F (e.g., Epiclon EXA-835LV), multifunctional epoxy resins based on phenol-novolac resin, dicyclopentadiene-type epoxy resins (e.g., Epiclon HP-7200L), naphthalene-type epoxy resins, and the like, as well as mixtures of any two or more thereof.
  • epoxy-functionalized resins are contemplated for use herein, e.g., liquid-type epoxy resins based on bisphenol A, solid-type epoxy resins based on bisphenol A, liquid-type epoxy resins based on bisphenol F (e.g., Epiclon EXA-835LV), multifunctional epoxy resins based on phenol-
  • Exemplary epoxy-functionalized resins contemplated for use herein include the diepoxide of the cycloaliphatic alcohol, hydrogenated bisphenol A (commercially available as Epalloy 5000), a difunctional cycloaliphatic glycidyl ester of hexahydrophthallic anhydride (commercially available as Epalloy 5200), Epiclon EXA-835LV, Epiclon HP-7200L, and the like, as well as mixtures of any two or more thereof.
  • the epoxy component may include the combination of two or more different bisphenol based epoxies. These bisphenol based epoxies may be selected from bisphenol A, bisphenol F, or bisphenol S epoxies, or combinations thereof. In addition, two or more different bisphenol epoxies within the same type of resin (such A, F or S) may be used.
  • bisphenol epoxies contemplated for use herein include bisphenol-F type epoxies (such as RE-404-S from Nippon Kayaku, Japan, and EPICLON 830 (RE1801), 830S (RE1815), 830A (REI 826) and 830W from Dai Nippon Ink & Chemicals, Inc., and RSL 1738 and YL-983U from Resolution) and bisphenol-A-type epoxies (such as YL-979 and 980 from Resolution).
  • bisphenol-F type epoxies such as RE-404-S from Nippon Kayaku, Japan
  • EPICLON 830 RE1815
  • 830A REI 826
  • 830W from Dai Nippon Ink & Chemicals, Inc.
  • RSL 1738 and YL-983U from Resolution
  • bisphenol-A-type epoxies such as YL-979 and 980 from Resolution
  • the bisphenol epoxies available commercially from Dai Nippon and noted above are promoted as liquid undiluted epichlorohydrin-bisphenol F epoxies having much lower viscosities than conventional epoxies based on bisphenol A epoxies and have physical properties similar to liquid bisphenol A epoxies.
  • Bisphenol F epoxy has lower viscosity than bisphenol A epoxies, all else being the same between the two types of epoxies, which affords a lower viscosity and thus a fast flow underfill sealant material.
  • the EEW of these four bisphenol F epoxies is between 165 and 180. The viscosity at 25° C.
  • the hydrolyzable chloride content is reported as 200 ppm for RE1815 and 830W, and that for RE1826 as 100 ppm.
  • the bisphenol epoxies available commercially from Resolution and noted above are promoted as low chloride containing liquid epoxies.
  • the bisphenol A epoxies have a EEW (g/eq) of between 180 and 195 and a viscosity at 25° C. of between 100 and 250 cps.
  • the total chloride content for YL-979 is reported as between 500 and 700 ppm, and that for YL-980 as between 100 and 300 ppm.
  • the bisphenol F epoxies have a EEW (g/eq) of between 165 and 180 and a viscosity at 25° C. of between 30 and 60.
  • the total chloride content for RSL-1738 is reported as between 500 and 700 ppm, and that for YL-983U as between 150 and 350 ppm.
  • epoxy component of the disclosed compositions In addition to the bisphenol epoxies, other epoxy compounds are contemplated for use as the epoxy component of the disclosed compositions.
  • cycloaliphatic epoxies such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbonate, can be used.
  • monofunctional, difunctional or multifunctional reactive diluents may be used to adjust the viscosity and/or lower the Tg of the resulting resin material.
  • Exemplary reactive diluents include butyl glycidyl ether, cresyl glycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, and the like.
  • Epoxies suitable for use herein include polyglycidyl derivatives of phenolic compounds, such as those available commercially under the tradename EPON, such as EPON 828, EPON 1001, EPON 1009, and EPON 1031 from Resolution; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; and BREN-S from Nippon Kayaku.
  • Other suitable epoxies include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, the latter of such as DEN 431, DEN 438, and DEN 439 from Dow Chemical.
  • Cresol analogs are also available commercially under the tradename ARALDITE, such as ARALDITE ECN 1235, ARALDITE ECN 1273, and ARALDITE ECN 1299 from Ciba Specialty Chemicals Corporation.
  • SU-8 is a bisphenol A-type epoxy novolac available from Resolution.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F.I.C. Corporation; ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510 from Ciba Specialty Chemicals and PGA-X and PGA-C from the Sherwin-Williams Co.
  • Appropriate monofunctional epoxy coreactant diluents for optional use herein also include those that have a viscosity which is lower than that of the epoxy component, ordinarily, less than about 250 cps.
  • the monofunctional epoxy coreactant diluents may have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C 6-28 alkyl glycidyl ethers, C 6-28 fatty acid glycidyl esters, C 6-28 alkylphenol glycidyl ethers, and the like.
  • the epoxy resin is novolac epoxy EEW 200, novolac epoxy EEW 300, or novolac epoxy EEW 140.
  • the epoxy resin is a compound represented by
  • epoxy resins are included in amounts ranging from about 1 wt. % to about 30 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 1 wt. % to about 25 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 1 wt. % to about 20 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 1 wt. % to about 15 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 3 wt. % to about 15 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 1 wt.
  • epoxy resins are included in amounts ranging from about 5 wt. % to about 20 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 5 wt. % to about 15 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 10 wt. % to about 20 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 15 wt. % to about 30 wt. %. In some embodiments, epoxy resins are included in amounts ranging from about 15 wt. % to about 25 wt. %.
  • epoxy resins are included in amounts ranging from about 10 wt. % to about 15 wt. %. In some embodiments, epoxy resins are included in about 10 wt. %, about 11 wt. %, about 12 wt. %, about 13 wt. %, about 14 wt. %, about 15 wt. %, about 16 wt. %, about 17 wt. %, about 18 wt. %, about 19 wt. %, about 20 wt. %, about 21 wt. %, about 22 wt. %, about 23 wt. %, about 24 wt. %, about 25 wt. %, about 26 wt. %, about 27 wt. %, about 28 wt. %, about 29 wt. %, about 30 wt. %.
  • film forming binder resins are included in amounts ranging from about 1 wt. % to about 25 wt. %. In some embodiments, film forming binder resins are included in amounts ranging from about 1 wt. % to about 20 wt. %. In some embodiments, film forming binder resins are included in amounts ranging from about 10 wt. % to about 20 wt. %. In some embodiments, film forming binder resins are included in amounts ranging from about 13 wt. % to about 18 wt. %. In some embodiments, film forming binder resins are included in amounts ranging from about 14 wt. % to about 16 wt. %.
  • film forming binder resins are included in amounts of about 10 wt. %, about 11 wt. %, about 12 wt. %, about 13 wt. %, about 14 wt. %, about 15 wt. %, about 16 wt. %, about 17 wt. %, about 18 wt. %, about 19 wt. %, about 20 wt. %, about 21 wt. %, about 22 wt. %, about 23 wt. %, about 24 wt. %, or about 25 wt. %.
  • compositions of the disclosure include among other constituents one or more (meth)acrylate-containing resins.
  • the (meth)acrylate resin is represented by
  • (meth)acrylate-containing resins are included in amounts ranging from about 1 wt. % to about 20 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 1 wt. % to about 15 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 3 wt. % to about 15 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 1 wt. % to about 5 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 5 wt.
  • (meth)acrylate-containing resins are included in amounts ranging from about 5 wt. % to about 15 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 10 wt. % to about 20 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 10 wt. % to about 15 wt. %. In some embodiments, (meth)acrylate-containing resins are included in amounts ranging from about 12 wt. % to about 17 wt. %.
  • compositions of the disclosure include among other constituents one or more inorganic fillers.
  • the filler is an electrically non-conductive filler, such as silica.
  • the filler is (or comprises) silica, calcium silicate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), magnesium oxide (MgO), aluminum nitride (AlN), boron nitride (BN), carbon nanotubes, diamond, clay, aluminosilicate, and the like, as well as mixtures of any two or more thereof.
  • the inorganic filler is an inorganic non-conductive filler comprising particles having a maximum particle size of 5 ⁇ m or less than 5 ⁇ m.
  • the filler has a particle size in the from about 0.1 ⁇ m to about 5 ⁇ m or from 0.1 ⁇ m to 5 ⁇ m.
  • filler loadings are sufficient to meet underfill material requirements.
  • fillers are included in an amount ranging from about 10 wt. % to about 70 wt. %.
  • fillers are included in an amount ranging from about 20 wt. % to about 60 wt. %.
  • fillers are included in an amount ranging from about 25 wt.
  • fillers are included in an amount ranging from about 30 wt. % to about 50 wt. %. In some embodiments, fillers are included in an amount ranging from about 35 wt. % to about 45 wt. %. In some embodiments, fillers are included in an amount ranging from about 35 wt. %, about 36 wt. %, about 37 wt. %, about 38 wt. %, about 39 wt. %, about 40 wt. %, about 41 wt. %, about 42 wt. %, about 43 wt. %, about 44 wt. %, or about 45 wt. %.
  • compositions of the disclosure include among other constituents one or more additives selected from the group consisting of adhesion promoters and film formers.
  • adhesion promoters refers to compounds that enhance the adhesive properties of the formulation to which they are introduced.
  • Adhesion promoters can be organic or inorganic compounds and can include combinations thereof.
  • Non-limiting examples of adhesion promoters include organo-zirconate compounds, organo-titanate compounds, and silane coupling agents.
  • the adhesion promoter is Z6040 from Dow.
  • film formers refers to compounds that assist in the formation of a film, such as (as a non-limiting example), by increasing the viscosity of the combined materials.
  • film formers including elastomeric additive components such as, but not limited to, copolymeric ethylene acrylic elastomers, natural or synthetic rubbers such as substituted polyethylenes, resins such as polyvinyl butyral resins and chlorosulfonated polyethylene synthetic rubbers (CSM), partially cross-linked butyl rubber compounds such as butyl rubber products commercially available from Royal Elastomers of New Jersey under the brand names KALAR®, DPR®, ISOLENE® and KALENE®, and ethylene acrylic elastomeric materials such as Vamac®, which is commercially available from the DuPont Corporation.
  • elastomeric additive components such as, but not limited to, copolymeric ethylene acrylic elastomers, natural or synthetic rubbers such as substituted polyethylenes, resins such as polyvinyl butyral resins and
  • film formers include, but are not limited to, acrylic polymers such as copolymers of butyl acrylate-ethyl acrylate-acetonitrile and copolymers of ethyl acrylate-acetonitrile (e.g., polymers comprising glycidyl functional groups), such as copolymers available from Nagase JP.
  • acrylic polymers such as copolymers of butyl acrylate-ethyl acrylate-acetonitrile and copolymers of ethyl acrylate-acetonitrile (e.g., polymers comprising glycidyl functional groups), such as copolymers available from Nagase JP.
  • film formers are included in an amount ranging from about 15 to about 40 wt. %. In some embodiments, film formers are included in an amount ranging from about 15 to about 30 wt. %. In some embodiments, film formers are included in an amount ranging from about 20 to about 30 wt. %. In some embodiments, film formers are included in an amount ranging from about 22 to about 28 wt. %. In some embodiments, film formers are included in an amount ranging from about 23 to about 26 wt. %. In some embodiments, film formers are included in an amount ranging from about 23 to about 25 wt. %. In some embodiments, film formers are included in about 24 wt. %, about 25 wt. %, or about 26 wt. %.
  • compositions of the disclosure further comprise one or more fluxing agents.
  • fluxing agents refers to reducing agents which prevent oxides from forming on the surface of a molten metal.
  • Non-limiting examples of fluxing agents include compounds having at least one (meth)acrylate group and at least one carboxylic acid group, carboxylic acids (including, but not limited to, compounds having one or more acrylic acid functional groups, rosin gum, dodecanedioic acid (commercially available as Corfree M2 from Aldrich), adipic acid, sebasic acid, polysebasic polynhydride, maleic acid, tartaric acid, citric acid, and the like), alcohols, hydroxyl acid and hydroxyl base, polyols (including, but not limited to, ethylene glycol, glycerol, 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol, D-ribose, D-cellobiose, cellulose, 3-cyclohexene-1,1-dimethanol, and the like
  • fluxing agents are included in an amount ranging from about 1 to about 10 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 1 to about 5 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 5 to about 10 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 2 to about 8 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 3 to about 7 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 3 to about 5 wt. %.
  • fluxing agents are included in an amount ranging from about 3 to about 7 wt. %. In some embodiments, fluxing agents are included in an amount ranging from about 3 wt. %, about 4 wt. %, or about 5 wt. %.
  • aspects of the disclosure also relate to methods of preparing B-stage films and/or cured films.
  • the methods of preparing cured films comprise:
  • the methods of preparing cured films comprise:
  • the methods of preparing cured films comprise:
  • the one or more resins selected from the group consisting of maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins, wherein the maleimide-containing resins, nadimide-containing resins, itaconimide-containing resins, epoxy resins, (meth)acrylate-containing resins, and phenolic-containing resins are those disclosed elsewhere herein and, optionally, in the amounts disclosed elsewhere herein.
  • the one or more imidazoles are those disclosed elsewhere herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more imidazoles are those disclosed elsewhere herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more inorganic fillers are those disclosed elsewhere herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more additives selected from the group consisting of adhesion promoters and film formers are those disclosed elsewhere herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more fluxing agents are those disclosed elsewhere herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more fluxing agents are compounds having at least one (meth)acrylate group and at least one carboxylic acid group and, optionally, are present in the amounts disclosed elsewhere herein.
  • the one or more fluxing agents are one or more fluxing agents described herein and, optionally, are present in the amounts disclosed elsewhere herein.
  • films prepared according to methods of preparing cured films disclosed herein have the physical properties of films disclosed elsewhere herein.
  • films prepared according to methods of preparing films disclosed herein have one or more of the Tg as measured by DMA, storage modulus at 25° C., storage modulus at 230° C., storage modulus at 250° C., CTE, DSC onset temperature as measured by DSC with a 10° C./min ramping rate, and minimum film melt viscosity measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 of cured films disclosed elsewhere herein.
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • films prepared according to methods of preparing films disclosed herein have the following physical properties:
  • compositions according to the disclosure including components thereof, are presented in Table 1.
  • Imidazole A is 4-methyl-2-phenyl-1H-imidazole-5-methanol.
  • Imidazole B is 2-phenyl-4,5-dihydroxymethylimidazole.
  • Example 5 Example 6
  • Example 7 Resin Film forming binder 14.56 14.56 14.56 resin Filler Silica filler 40
  • Epoxy Polymeric epoxy (EEW 310) 10 10 10 Cresol novolac epoxy 12.96 12.96 resin (EEW 200) Biphenyl aralkyl epoxy 12.96 resin (EEW 276)
  • BMI resin (maleimide equivalent weight 185)
  • BMI resin maleimide equivalent weight 221)
  • BMI resin maleimide 15.35 15.35 15.35 equivalent weight 393
  • Adhesion promoter 1 1 1 Curing Agent Imidazole A 2 3.14 Imidazole B 3.14
  • compositions according to the disclosure are presented in Table 2.
  • Imidazole A is 4-methyl-2-phenyl-1H-imidazole-5-methanol.
  • Imidazole C is 2-phenylimidazole.
  • Imidazole D is 2-ethyl-4-methyl-1H-imidazole-1-propanenitrile.
  • Example 2 Example 3
  • Example 4 Resin Film 10.0 50.0 30.5 10.0 9.4 forming binder resin Filler Silica filler, 40 25 40 0.3 ⁇ m Silica filler, 40 2 ⁇ m Fumed 2 silica filler Monomers Epoxy 27.52 30.13 24.20 14.56 18.4 BMI 15.35 7.2 15.23 15
  • Additives Fluxing 4 3 3 agent Z6040 1.13 1.03 0.8 1.13 1.13 adhesion promoter Curing Dicumyl 0.45 agent peroxide Imidazole 2.00 (Imidazole 0.01 (Imidazole 3.00 (Imidazole A) C) D) 4,4-DDS 4.00 5.10 Other 0.33 2.20 amines
  • Example 1 Example 2
  • Example 3 Example 4
  • N/A viscosity temperature (° C.) DMA Tg (° C.) 277 152 272 155 231 Modulus at 5.043 1.347 2.322 6.628 7.167 25° C.
  • composition of each of Inventive Example 8, Comparative Example 1, and Comparative Example 4 comprised an imidazole curing agent, but the composition of Comparative Example 1 and the composition of Comparative Example 4 did not comprise an imidazole with at least two electron withdrawing groups, whereas the composition of Inventive Example 8 did comprise an imidazole with at least two electron withdrawing groups.
  • the composition of Inventive Example 8 had a ⁇ T from the DSC onset temperature to the DSC peak temperature that was less than 20° C., unlike the composition of Comparative Example 1 (rounded to the nearest integer).
  • the composition of Inventive Example 8 had a DSC onset temperature of from 130° C. to 250° C. as measured by DSC with a 10° C./min ramping rate (specifically, of 148.40° C.) and a minimum film melt viscosity of from 10 Pa ⁇ s to 10,000 Pa ⁇ s as measured using a DHR2 rheometer with a 10° C./min ramping rate in N 2 (specifically, of 5,936 Pa ⁇ s).
  • composition of Inventive Example 8 demonstrated good solder interconnect formation, no material entrapment, and no voids, and it also demonstrated a higher Tg, lower CTE, and better high temperature properties compared to the Comparative Examples. Although the composition of Comparative Example 3 also demonstrated good solder interconnect formation, no material entrapment, and no voids, the compositions of Comparative Examples 1-4 all demonstrated inferior high temperature properties compared Inventive Example 8. The compositions of Comparative Examples 1, 2, and 4 were deemed unsuitable for thermocompression bonding processes.
  • compositions comprising an imidazole with latent thermal activity such as an imidazole comprising at least two electron-withdrawing groups
  • compositions comprising an imidazole without latent thermal activity such as an imidazole with one or no electron-withdrawing groups, or compositions that lack an imidazole, are less suitable for thermocompression bonding processes.
  • DSC, melt viscosity, DMA, and TMA data associated with exemplary composition Inventive Example 3 are provided in FIG. 1 , FIG. 2 , FIG. 3 , and FIG. 4 , respectively.
  • DSC, melt viscosity, DMA, and TMA data associated with exemplary composition Inventive Example 8 are provided in FIG. 5 , FIG. 6 , FIG. 7 , and FIG. 8 , respectively.

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